Pigmented polymer particles and methods of production and uses thereof

ABSTRACT

Pigmented polymer particles may comprise a thermoplastic polymer and a pigment, wherein at least some of the pigmented polymer particles have a morphology according to (a), (b), (c), or any combination thereof: (a) the pigment having a coating comprising the thermoplastic polymer and the coated pigment adhered to a thermoplastic polymer particle, (b) the pigment being embedded in an outer surface of the thermoplastic polymer particle, and (c) the pigment being encapsulated by the thermoplastic polymer particle. The pigmented polymer particles, especially the highly spherical pigmented polymer particles, may be useful, among other things, as starting material for additive manufacturing. For example, a method may comprise: depositing, upon a surface, the foregoing pigmented polymer particles optionally in combination with other thermoplastic polymer particles; and once deposited, heating at least a portion of the particles to promote consolidation thereof and form a consolidated body.

TECHNICAL FIELD

The present disclosure relates to particles that comprise pigments and athermoplastic polymer. Said particles are referred to as pigmentedpolymer particles. The present disclosure further relates to the methodsof making and using such pigmented polymer particles.

BACKGROUND

Thermoplastic polymers are often used to make extruded objects likefilms, bags, particles, and filaments. Many thermoplastic polymers areoff-white colored polymers that have the ability to withstand elevatedtemperatures and/or low temperatures without loss of physicalproperties. Therefore, objects formed with thermoplastic polymers can beused in demanding applications like power tools, automotive parts,gears, and appliance parts. In some instances, the application may callfor the thermoplastic polymer-made part to be colored or have othervisible identifiers like phosphorescence. For example, phosphorescence,a color pattern, or a color combination can be used to identify parts asan anti-counterfeiting measure.

Because pigments are particulates, pigments can be difficult tohomogeneously mix in the thermoplastic polymers. One application wherehomogeneous incorporation of pigments is especially important is therapidly growing technology area of three-dimensional (3-D) printing,also known as additive manufacturing. Although 3-D printing hastraditionally been used for rapid prototyping activities, this techniqueis being increasingly employed for producing commercial and industrialobjects, which may have entirely different structural and mechanicaltolerances than do rapid prototypes.

3-D printing operates by depositing either (a) small droplets or streamsof a melted or solidifiable material or (b) powder particulates inprecise deposition locations for subsequent consolidation into a largerobject, which may have any number of complex shapes. Such deposition andconsolidation processes typically occur under the control of a computerto afford layer-by-layer buildup of the larger object. In a particularexample, consolidation of powder particulates may take place in a 3-Dprinting system using a laser to promote selective laser sintering(SLS).

SUMMARY OF THE INVENTION

The present disclosure relates to pigmented polymer particles and themethods of making and using such particles. The pigmented polymerparticles described herein, especially the highly spherical pigmentedpolymer particles, may be useful, among other things, as startingmaterial for additive manufacturing. Further, the visual properties(e.g., color, combination of colors, phosphorescence, and the like) maybe used for identifying objects, tracking objects, authenticatingobjects, and/or determining the health of objects made from thepigmented polymer particles.

Disclosed herein are compositions that comprise: pigmented polymerparticles comprising a thermoplastic polymer and a pigment having amelt-emulsified morphology.

Disclosed herein are compositions that comprise: pigmented polymerparticles comprising a thermoplastic polymer and a pigment, wherein atleast some of the pigmented polymer particles have a morphologyaccording to (a), (b), (c), or any combination thereof: (a) the pigmenthaving a coating comprising the thermoplastic polymer and the coatedpigment adhered to a thermoplastic polymer particle, (b) the pigmentbeing embedded in an outer surface of the thermoplastic polymerparticle, and (c) the pigment being encapsulated by the thermoplasticpolymer particle.

Disclosed herein are methods that comprise: depositing, upon a surface,the either or both of the foregoing pigmented polymer particlesoptionally in combination with other thermoplastic polymer particles;and once deposited, heating at least a portion of the particles topromote consolidation thereof and form a consolidated body.

Disclosed herein are methods that comprise: mixing a mixture comprisinga thermoplastic polymer, a carrier fluid that is immiscible with thethermoplastic polymer, a pigment, and optionally an emulsion stabilizerat a temperature greater than a melting point or softening temperatureof the thermoplastic polymer and at a shear rate sufficiently high todisperse the thermoplastic polymer in the carrier fluid; cooling themixture to below the melting point or softening temperature of thethermoplastic polymer to form pigmented polymer particles comprising athermoplastic polymer and a pigment having a melt-emulsified morphology;and separating the pigmented polymer particles from the carrier fluid.

Disclosed herein are methods that comprise: mixing a mixture comprisinga thermoplastic polymer, a carrier fluid that is immiscible with thethermoplastic polymer, a pigment, and optionally an emulsion stabilizerat a temperature greater than a melting point or softening temperatureof the thermoplastic polymer and at a shear rate sufficiently high todisperse the thermoplastic polymer in the carrier fluid; cooling themixture to below the melting point or softening temperature of thethermoplastic polymer to form pigmented polymer particles comprising athermoplastic polymer and a pigment, wherein at least some of thepigmented polymer particles have a morphology according to (a), (b),(c), or any combination thereof: (a) the pigment having a coatingcomprising the thermoplastic polymer and the coated pigment adhered to athermoplastic polymer particle, (b) the pigment being embedded in anouter surface of the thermoplastic polymer particle, and (c) the pigmentbeing encapsulated by the thermoplastic polymer particle; and separatingthe pigmented polymer particles from the carrier fluid.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures are included to illustrate certain aspects of theembodiments, and should not be viewed as exclusive embodiments. Thesubject matter disclosed is capable of considerable modifications,alterations, combinations, and equivalents in form and function, as willoccur to those skilled in the art and having the benefit of thisdisclosure.

FIG. 1 is a flow chart of a nonlimiting example method 100 of thepresent disclosure.

FIGS. 2 and 3 are scanning electron micrographs of Samples 1-2 and 1-3,respectively, illustrating polymer coated pigment being adhered to asurface of the polymer particle.

FIGS. 4 and 5 are cross-sectional scanning electron micrographs (samplesfixed in epoxy resin and cryo-microtomed before imaging) of Sample 1-2illustrating (a) pigment not adhered to, embedded in, or encapsulated bya polymer particle and (b) pigment embedded in a surface of a polymerparticle.

FIGS. 6 and 7 are scanning electron micrographs of Sample 3-1illustrating what is likely polymer coated pigment being adhered to asurface of the polymer particle.

FIGS. 8 and 9 are cross-sectional scanning electron micrographs (samplesfixed in epoxy resin and cryo-microtomed before imaging) illustrating(a) pigment embedded in a surface of the polymer particle and (b)pigment encapsulated in the polymer particle.

DETAILED DESCRIPTION

Three-dimensional (3-D) printing, also known as additive manufacturing,is a rapidly growing technology area. Although 3-D printing hastraditionally been used for rapid prototyping activities, this techniqueis being increasingly employed for producing commercial and industrialobjects, which may have entirely different structural and mechanicaltolerances than do rapid prototypes.

The present disclosure relates to polymer particles that comprisepigments and a thermoplastic polymer. Said particles are referred to aspigmented polymer particles. The pigmented polymer particles may includeparticles having a morphology according to (a), (b), (c), or anycombination thereof: (a) the pigment having a coating comprising thethermoplastic polymer and the coated pigment adhered to a thermoplasticpolymer particle, (b) the pigment being embedded in an outer surface ofthe thermoplastic polymer particle, and (c) the pigment beingencapsulated by the thermoplastic polymer particle.

The pigmented polymer particles described herein, especially the highlyspherical pigmented polymer particles, may be useful, among otherthings, as starting material for additive manufacturing. Further, thecolor and/or phosphorescence imparted by the pigments can be used foridentifying objects, tracking objects, authenticating objects, and/ordetermining the health of objects made from the pigmented polymerparticles.

Definitions and Test Methods

As used herein, the term “immiscible” refers to a mixture of componentsthat, when combined, form two or more phases that have less than 5 wt %solubility in each other at ambient pressure and at room temperature orthe melting point of the component if it is solid at room temperature.For example, polyethylene oxide having 10,000 g/mol molecular weight isa solid room temperature and has a melting point of 65° C. Therefore,said polyethylene oxide is immiscible with a material that is liquid atroom temperature if said material and said polyethylene oxide have lessthan 5 wt % solubility in each other at 65° C.

As used herein, the term “pigment” refers to a particle that absorbsand/or refracts ultraviolet or visible light.

As used herein, the term “phosphorescence” and grammatical variationsthereof refer to luminescence that persists at least 10 nanosecondsafter the exciting cause (e.g., broad spectrum light, ultravioletwavelength lights of light, a specific wavelength of light, or the like)is removed.

As used herein, a “phosphorescent pigment” is a pigment that whenexposed to an exciting cause will phosphoresce.

As used herein, the term “thermoplastic polymer” refers to a plasticpolymer material that softens and hardens reversibly on heating andcooling. Thermoplastic polymers encompass thermoplastic elastomers.

As used herein, the term “elastomer” refers to a copolymer comprising acrystalline “hard” section and an amorphous “soft” section. In the caseof a polyurethane, the crystalline section may include a portion of thepolyurethane comprising the urethane functionality and optional chainextender group, and the soft section may include the polyol, forinstance.

As used herein, the term “polyurethane” refers to a polymeric reactionproduct between a diisocyanate, a polyol, and an optional chainextender.

As used herein, the term “oxide” refers to both metal oxides andnon-metal oxides. For purposes of the present disclosure, silicon isconsidered to be a metal.

As used herein, the term “embed” relative to particles (e.g.,nanoparticles and/or pigments) and a surface of a polymer particlerefers to the particle being at least partially extending into thesurface of the polymer particle such that polymer is in contact with thenanoparticle to a greater degree than would be if the nanoparticle weresimply laid on the surface of the polymer particle.

As used herein, the term “encapsulated” relative to particles (e.g.,nanoparticles and/or pigments) and polymer particles refers to theparticle being enclosed by the polymer particle. That is, portions ofsaid particles (e.g., nanoparticles and/or pigments) do not extendbeyond the surface of the polymer particle. The term “encapsulate” doesnot imply a degree to which the surface of the particle (e.g.,nanoparticles and/or pigments) surface is contact with polymer. Forexample, the particle (e.g., nanoparticles and/or pigments) may be atleast partially in a void within the polymer particle and only a portionof the surface of the particle be in contact with the polymer.

Herein, D10, D50, D90, and diameter span are primarily used herein todescribe particle sizes. As used herein, the term “D10” refers to adiameter at which 10% of the sample (on a volume basis unless otherwisespecified) is comprised of particles having a diameter less than saiddiameter value. As used herein, the term “D50” refers to a diameter atwhich 50% of the sample (on a volume basis unless otherwise specified)is comprised of particles having a diameter less than said diametervalue. As used herein, the term “D90” refers to a diameter at which 90%of the sample (on a volume basis unless otherwise specified) iscomprised of particles having a diameter less than said diameter value.

As used herein, the terms “diameter span” and “span” and “span size”when referring to diameter provides an indication of the breadth of theparticle size distribution and is calculated as (D90−D10)/D50 (againeach D-value is based on volume, unless otherwise specified).

Particle size can be determined by light scattering techniques using aMalvern MASTERSIZER™ 3000 or analysis of optical digital micrographs.Unless otherwise specified, light scattering techniques are used foranalyzing particle size.

For light scattering techniques, the control samples were glass beadswith a diameter within the range of 15 μm to 150 μm under the tradenameQuality Audit Standards QAS4002™ obtained from Malvern Analytical Ltd.Samples were analyzed as dry powders, unless otherwise indicated. Theparticles analyzed were dispersed in air and analyzed using the AERO Sdry powder dispersion module with the MASTERSIZER™ 3000. The particlesizes were derived using instrument software from a plot of volumedensity as a function of size.

Particle size measurement and diameter span can also be determined byoptical digital microscopy. The optical images are obtained using aKeyence VHX-2000 digital microscope using version 2.3.5.1 software forparticle size analysis (system version 1.93).

As used herein, when referring to sieving, pore/screen sizes aredescribed per U.S.A. Standard Sieve (ASTM E11-17).

As used herein, the terms “circularity” and “sphericity” relative to theparticles refer to how close the particle is to a perfect sphere. Todetermine circularity, optical microscopy images are taken of theparticles. The perimeter (P) and area (A) of the particle in the planeof the microscopy image is calculated (e.g., using a SYSMEX FPIA 3000particle shape and particle size analyzer, available from MalvernInstruments). The circularity of the particle is C_(EA)/P, where C_(EA)is the circumference of a circle having the area equivalent to the area(A) of the actual particle.

As used herein, the term “shear” refers to stirring or a similar processthat induces mechanical agitation in a fluid.

As used herein, the term “aspect ratio” refers to length divided bywidth, wherein the length is greater than the width.

The melting point of a polymer, unless otherwise specified, isdetermined by ASTM E794-06(2018) with 10° C./min ramping and coolingrates.

The softening temperature or softening point of a polymer, unlessotherwise specified, is determined by ASTM D6090-17. The softeningtemperature can be measured by using a cup and ball apparatus availablefrom Mettler-Toledo using a 0.50 gram sample with a heating rate of 1°C./min.

Angle of repose is a measure of the flowability of a powder. Angle ofrepose measurements were determined using a Hosokawa Micron PowderCharacteristics Tester PT-R using ASTM D6393-14 “Standard Test Methodfor Bulk Solids” Characterized by Carr Indices.”

Hausner ratio (H_(r)) is a measure of the flowability of a powder and iscalculated by H_(r)=ρ_(tap)/ρ_(bulk), where ρ_(bulk) is the bulk densityper ASTM D6393-14 and ρ_(tap) is the tapped density per ASTM D6393-14.

As used herein, viscosity of carrier fluids are the kinematic viscosityat 25° C., unless otherwise specified, measured per ASTM D445-19. Forcommercially procured carrier fluids (e.g., polydimethylsiloxane oil),the kinematic viscosity data cited herein was provided by themanufacturer, whether measured according to the foregoing ASTM oranother standard measurement technique.

Pigmented Polymer Particles and Methods of Making

The methods and compositions described herein relate to pigmentedpolymer particles. The pigments are included in the melt emulsionproduction of the pigmented polymer particles. Pigmented polymerparticles may comprise polymer particles that include a pigment and athermoplastic polymer. Depending on, among other things, the pigmentcomposition, the thermoplastic polymer composition, and the meltemulsification process parameters, the morphology of the pigmentedpolymer particles may vary. For example, the thermoplastic polymer mayform a coating on the pigment, and the coated pigment may adhere to thesurface of a thermoplastic polymer particle. In another example, thepigment may become embedded in a surface of the thermoplastic polymerparticle. In such instances, the pigment embedded in the thermoplasticpolymer particle may or may not have a coating comprising thethermoplastic polymer. In yet another example morphology, the pigmentmay become encapsulated in the thermoplastic polymer particle. Anycombination of the foregoing may also be present and may be referred toherein as melt-emulsification morphologies. Further, the compositionsand methods described herein do not require that all thermoplasticpolymer particles have a pigment accompanying a thermoplastic polymerparticle. That is, the compositions produced and methods describedherein may include a mixture of particles that include one or more of:(a) thermoplastic polymer particles (i.e., particles comprising thethermoplastic polymer) having no pigment associated therewith (e.g., athermoplastic polymer particle not having a pigment adhered thereto,embedded therein, or encapsulated thereby), (b) pigmented polymerparticles that include pigments and a thermoplastic polymer having amelt-emulsified morphology, and (c) thermoplastic polymer coated pigmentnot associated with thermoplastic polymer particles (e.g., thermoplasticpolymer coated pigment not adhered to, embedded in, or encapsulated by athermoplastic polymer particle). The (b) pigmented polymer particlesthat include pigments and a thermoplastic polymer having amelt-emulsified morphology may include one or more of: (b1)thermoplastic polymer particles having pigment adhered thereto via thepolymer (e.g., the pigment having a coating comprising the thermoplasticpolymer and the coated pigment is adhered to an outer surface of athermoplastic polymer particle), (b2) thermoplastic polymer particleshaving pigment embedded in a surface of the polymer particles, and (b3)thermoplastic polymer particles having pigment encapsulated in thepolymer particles, where a single particle may have any combination of(b1), (b2), and (b3).

Without being limited by theory, it is believed that the meltemulsification process creates a more intimate combination between thethermoplastic polymer and the pigment, which allows for the pigment tomore readily associate, by one or more of a variety of morphologies,with a polymer particle. The pigmented polymer particles having amelt-emulsified morphology may improve the integrity (e.g., reduced voidspace and/or less deformation) of the resultant SLS additivemanufactured article while also providing comparable color and/orphosphorescence as compared to an admix of pigment and polymerparticles.

FIG. 1 is a flow chart of a nonlimiting example method 100 of thepresent disclosure. Thermoplastic polymer 102, carrier fluid 104,optionally emulsion stabilizer 106, and pigment 108 are combined 110 toproduce a mixture 112. The components 102, 104, 106, and 108 can beadded in any order and include mixing and/or heating during the processof combining 110 the components 102, 104, 106, and 108.

The mixture 112 is then processed 114 by applying sufficiently highshear to the mixture 112 at a temperature greater than the melting pointor softening temperature of the thermoplastic polymer 102 to form a meltemulsion 116. Because the temperature is above the melting point orsoftening temperature of the thermoplastic polymer 102, thethermoplastic polymer 102 becomes a polymer melt. The shear rate shouldbe sufficient enough to disperse the polymer melt in the carrier fluid104 as droplets (i.e., the polymer emulsion 116). Without being limitedby theory, it is believed that, all other factors being the same,increasing shear should decrease the size of the droplets of the polymermelt in the carrier fluid 104. However, at some point there may bediminishing returns on increasing shear and decreasing droplet size orthere may be disruptions to the droplet contents that decrease thequality of particles produced therefrom.

The melt emulsion 116 inside and/or outside the mixing vessel is thencooled 118 to solidify the polymer droplets into pigmented polymerparticles 124 (also referred to as solidified pigmented polymerparticles). The thermoplastic polymer particles 124 comprise athermoplastic polymer. At least some of the pigmented polymer particles124/130 comprise the thermoplastic polymer (composed of thethermoplastic polymer 102) and pigment 108 a having a melt-emulsifiedmorphology. The melt-emulsified morphology may comprises at least one ofthe following: (a) the pigment having a coating comprising thethermoplastic polymer and the coated pigment is adhered to an outersurface of a thermoplastic polymer particle (i.e., particles thatcomprise the thermoplastic particle), (b) the pigment being embedded inan outer surface of a thermoplastic polymer particle, and (c) thepigment being encapsulated by a thermoplastic polymer particle, where asingle pigmented polymer particle may have any combination of (a), (b),and (c). Preferably, the pigmented polymer particles 124/130 includeparticles having morphologies according to (b) and/or (c). Further, asdescribed above, other components of the product in addition to thepigmented polymer particles 124 may include pigment 108 coated in thethermoplastic polymer 102 but not associated with a polymer particleand/or polymer particles without pigment 108 associated therewith.

The cooled mixture 120 can then be treated 122 to isolate the pigmentedpolymer particles 124 from other components 126 (e.g., the carrier fluid104, excess emulsion stabilizer 106, and the like) and wash or otherwisepurify the pigmented polymer particles 124. The pigmented polymerparticles 124 comprise the thermoplastic polymer 102 and the pigment 108including particles with a melt-emulsified morphology, and, whenincluded, at least a portion of the emulsion stabilizer 106 coating theouter surface of the pigmented polymer particles 124. Further, theemulsion stabilizer 106 may coat at least a portion of a polymer coatingof the pigment 108, when coated pigment is produced. Emulsionstabilizers 106, or a portion thereof, may be deposited as coating,perhaps a uniform coating, on the pigmented polymer particles 124 (andcoated pigment, when produced). In some instances, which may bedependent upon non-limiting factors such as the temperature (includingcooling rate), the type of thermoplastic polymer 102, and the types andsizes of emulsion stabilizers 106, the nanoparticles of emulsionstabilizers 106 may become at least partially embedded within the outersurface of pigmented polymer particles 124. Even without embedmenttaking place, at least a portion of the nanoparticles within emulsionstabilizers 106 may remain robustly associated with pigmented polymerparticles 124 to facilitate their further use. In contrast, dry blendingalready formed thermoplastic polymer particulates (e.g., formed bycryogenic grinding or precipitation processes) with a flow aid likesilica nanoparticles does not result in a robust, uniform coating of theflow aid upon the thermoplastic polymer particulates (and coatedpigment, when produced).

The pigmented polymer particles 124 may optionally be further purified128 (described in more detail below) to yield purified pigmented polymerparticles 130.

The thermoplastic polymer 102 and carrier fluid 104 should be chosensuch that at the various processing temperatures (e.g., from roomtemperature to process temperature) the thermoplastic polymer 102 andcarrier fluid 104 are immiscible. An additional factor that may beconsidered is the differences in (e.g., a difference or a ratio of)viscosity at process temperature between the molten thermoplasticpolymer 102 and the carrier fluid 104. The differences in viscosity mayaffect droplet breakup and particle size distribution. Without beinglimited by theory, it is believed that when the viscosities of themolten thermoplastic polymer 102 and the carrier fluid 104 are toosimilar, the circularity of the product as a whole may be reduced wherethe particles are more ovular and more elongated structures areobserved.

Examples of thermoplastic polymers 102 include, but are not limited to,polyamides, polyurethanes, polyethylenes, polypropylenes, polyacetals,polycarbonates, polybutylene terephthalate (PBT), polyethyleneterephthalate (PET), polyethylene naphthalate (PEN), polytrimethyleneterephthalate (PTT), polyhexamethylene terephthalate, polystyrenes,polyvinyl chlorides, polytetrafluoroethenes, polyesters (e.g.,polylactic acid), polyethers, polyether sulfones, polyetheretherketones, polyacrylates, polymethacrylates, polyimides, acrylonitrilebutadiene styrene (ABS), polyphenylene sulfides, vinyl polymers,polyarylene ethers, polyarylene sulfides, polysulfones, polyetherketones, polyamide-imides, polyetherimides, polyetheresters, copolymerscomprising a polyether block and a polyamide block (PEBA or polyetherblock amide), grafted or ungrafted thermoplastic polyolefins,functionalized or nonfunctionalized ethylene/vinyl monomer polymer,functionalized or nonfunctionalized ethylene/alkyl (meth)acrylates,functionalized or nonfunctionalized (meth)acrylic acid polymers,functionalized or nonfunctionalized ethylene/vinyl monomer/alkyl(meth)acrylate terpolymers, ethylene/vinyl monomer/carbonyl terpolymers,ethylene/alkyl (meth)acrylate/carbonyl terpolymers,methylmethacrylate-butadiene-styrene (MBS)-type core-shell polymers,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM)block terpolymers, chlorinated or chlorosulphonated polyethylenes,polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene/vinylacetate)s, polybutadienes, polyisoprenes, styrenic block copolymers,polyacrylonitriles, silicones, and the like, and any combinationthereof. Copolymers comprising one or more of the foregoing may also beused in the methods and systems of the present disclosure.

The thermoplastic polymers 102 in the compositions and methods of thepresent disclosure may be elastomeric or non-elastomeric. Some of theforegoing examples of thermoplastic polymers 102 may be elastomeric ornon-elastomeric depending on the exact composition of the polymer. Forexample, polyethylene that is a copolymer of ethylene and propylene maybe elastomeric or not depending on the amount of propylene in thepolymer.

Thermoplastic elastomers generally fall within one of six classes:styrenic block copolymers, thermoplastic polyolefin elastomers,thermoplastic vulcanizates (also referred to as elastomeric alloys),thermoplastic polyurethanes, thermoplastic copolyesters, andthermoplastic polyamides (typically block copolymers comprisingpolyamide). Examples of thermoplastic elastomers can be found inHandbook of Thermoplastic Elastomers, 2nd ed., B. M. Walker and C. P.Rader, eds., Van Nostrand Reinhold, New York, 1988. Examples ofthermoplastic elastomers include, but are not limited to, elastomericpolyamides, polyurethanes, copolymers comprising a polyether block and apolyamide block (PEBA or polyether block amide), methylmethacrylate-butadiene-styrene (MBS)-type core-shell polymers,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM)block terpolymers, polybutadienes, polyisoprenes, styrenic blockcopolymers, and polyacrylonitriles), silicones, and the like.Elastomeric styrenic block copolymers may include at least one blockselected from the group of: isoprene, isobutylene, butylene,ethylene/butylene, ethylene-propylene, and ethylene-ethylene/propylene.More specific elastomeric styrenic block copolymer examples include, butare not limited to, poly(styrene-ethylene/butylene),poly(styrene-ethylene/butylene-styrene),poly(styrene-ethylene/propylene), styrene-ethylene/propylene-styrene),poly(styrene-ethylene/propylene-styrene-ethylene-propylene),poly(styrene-butadiene-styrene),poly(styrene-butylene-butadiene-styrene), and the like, and anycombination thereof.

Examples of polyamides include, but are not limited to, polycaproamide(nylon 6, polyamide 6, or PA6), poly(hexamethylene succinamide) (nylon4,6, polyamide 4,6, or PA4,6), polyhexamethylene adipamide (nylon 6,6,polyamide 6,6, or PA6,6), polypentamethylene adipamide (nylon 5,6,polyamide 5,6, or PA5,6), polyhexamethylene sebacamide (nylon 6,10,polyamide 6,10, or PA6,10), polyundecaamide (nylon 11, polyamide 11, orPA11), polydodecaamide (nylon 12, polyamide 12, or PA12), andpolyhexamethylene terephthalamide (nylon 6T, polyamide 6T, or PA6T),nylon 10,10 (polyamide 10,10 or PA10,10), nylon 10,12 (polyamide 10,12or PA10,12), nylon 10,14 (polyamide 10,14 or PA10,14), nylon 10,18(polyamide 10,18 or PA10,18), nylon 6,18 (polyamide 6,18 or PA6,18),nylon 6,12 (polyamide 6,12 or PA6,12), nylon 6,14 (polyamide 6,14 orPA6,14), nylon 12,12 (polyamide 12,12 or PA12,12), and the like, and anycombination thereof. Copolyamides may also be used. Examples ofcopolyamides include, but are not limited to, PA 11/10,10, PA 6/11, PA6,6/6, PA 11/12, PA 10,10/10,12, PA 10,10/10,14, PA 11/10,36, PA11/6,36, PA 10,10/10,36, PA 6T/6,6, and the like, and any combinationthereof. A polyamide followed by a first number comma second number is apolyamide having the first number of backbone carbons between thenitrogens for the section having no pendent ═O and the second number ofbackbone carbons being between the two nitrogens for the section havingthe pendent ═O. By way of nonlimiting example, nylon 6,10 is[NH—(CH₂)₆—NH—CO—(CH₂)₈—CO]_(n). A polyamide followed by number(s)backslash number(s) are a copolymer of the polyamides indicated by thenumbers before and after the backslash.

Examples of polyurethanes include, but are not limited to, polyetherpolyurethanes, polyester polyurethanes, mixed polyether and polyesterpolyurethanes, and the like, and any combination thereof. Examples ofthermoplastic polyurethanes include, but are not limited to,poly[4,4′-methylenebis(phenylisocyanate)-alt-1,4-butanediol/di(propyleneglycol)/polycaprolactone], ELASTOLLAN® 1190A (a polyether polyurethaneelastomer, available from BASF), ELASTOLLAN® 1190A10 (a polyetherpolyurethane elastomer, available from BASF), and the like, and anycombination thereof.

Compatibilizers may optionally be used to improve the blendingefficiency and efficacy thermoplastic polyester with one or morethermoplastic polymers. Examples of polymer compatibilizers include, butnot limited to, PROPOLDER™ MPP2020 20 (polypropylene, available fromPolygroup Inc.), PROPOLDER™ MPP2040 40 (polypropylene, available fromPolygroup Inc.), NOVACOM™ HFS2100 (maleic anhydride functionalized highdensity polyethylene polymer, available from Polygroup Inc.), KEN-REACT™CAPS™ L™ 12/L (organometallic coupling agent, available from KenrichPetrochemicals), KEN-REACT™ CAPOW™ L™ 12/H (organometallic couplingagent, available from Kenrich Petrochemicals), KEN-REACT™ LICA™ 12(organometallic coupling agent, available from Kenrich Petrochemicals),KEN-REACT™ CAPS™ KPR™ 12/LV (organometallic coupling agent, availablefrom Kenrich Petrochemicals), KEN-REACT™ CAPOW™ KPR™ 12/H(organometallic coupling agent, available from Kenrich Petrochemicals),KEN-REACT™ titanates & zirconates (organometallic coupling agent,available from Kenrich Petrochemicals), VISTAMAXX™ (ethylene-propylenecopolymers, available from ExxonMobil), SANTOPRENE™ (thermoplasticvulcanizate of ethylene-propylene-diene rubber and polypropylene,available from ExxonMobil), VISTALON™ (ethylene-propylene-diene rubber,available from ExxonMobil), EXACT™ (plastomers, available fromExxonMobil) EXXELOR™ (polymer resin, available from ExxonMobil),FUSABOND™ M603 (random ethylene copolymer, available from Dow),FUSABOND™ E226 (anhydride modified polyethylene, available from Dow),BYNEL™ 41E710 (coextrudable adhesive resin, available from Dow), SURLYN™1650 (ionomer resin, available from Dow), FUSABOND™ P353 (a chemicallymodified polypropylene copolymer, available from Dow), ELVALOY™ PTW(ethylene terpolymer, available from Dow), ELVALOY™ 3427AC (a copolymerof ethylene and butyl acrylate, available from Dow), LOTADER™ AX8840(ethylene acrylate-based terpolymer, available from Arkema), LOTADER™3210 (ethylene acrylate-based terpolymer, available from Arkema),LOTADER™ 3410 (ethylene acrylate-based terpolymer, available fromArkema), LOTADER™ 3430 (ethylene acrylate-based terpolymer, availablefrom Arkema), LOTADER™ 4700 (ethylene acrylate-based terpolymer,available from Arkema), LOTADER™ AX8900 (ethylene acrylate-basedterpolymer, available from Arkema), LOTADER™ 4720 (ethyleneacrylate-based terpolymer, available from Arkema), BAXXODUR™ EC 301(amine for epoxy, available from BASF), BAXXODUR™ EC 311 (amine forepoxy, available from BASF), BAXXODUR™ EC 303 (amine for epoxy,available from BASF), BAXXODUR™ EC 280 (amine for epoxy, available fromBASF), BAXXODUR™ EC 201 (amine for epoxy, available from BASF),BAXXODUR™ EC 130 (amine for epoxy, available from BASF), BAXXODUR™ EC110 (amine for epoxy, available from BASF), styrenics, polypropylene,polyamides, polycarbonate, EASTMAN™ G-3003 (a maleic anhydride graftedpolypropylene, available from Eastman), RETAIN™ (polymer modifieravailable from Dow), AMPLIFY TY™ (maleic anhydride grafted polymer,available from Dow), INTUNE™ (olefin block copolymer, available fromDow), and the like and any combination thereof.

The thermoplastic polymers 102 may have a melting point or softeningtemperature of about 50° C. to about 450° C. (or about 50° C. to about125° C., or about 100° C. to about 175° C., or about 150° C. to about280° C., or about 200° C. to about 350° C., or about 300° C. to about450° C.).

The thermoplastic polymers 102 may have a glass transition temperature(ASTM E1356-08(2014) with 10° C./min ramping and cooling rates) of about−50° C. to about 400° C. (or about −50° C. to about 0° C., or about −25°C. to about 50° C., or about 0° C. to about 150° C., or about 100° C. toabout 250° C., or about 150° C. to about 300° C., or about 200° C. toabout 400° C.).

The thermoplastic polymers 102 may optionally comprise an additive.Typically, the additive would be present before addition of thethermoplastic polymers 102 to the mixture 110. Therefore, in thethermoplastic polymer melt droplets and resultant thermoplastic polymerparticles, the additive is dispersed throughout the thermoplasticpolymer. Accordingly, for clarity, this additive is referred to hereinas an “internal additive.” The internal additive may be blended with thethermoplastic polymer just prior to making the mixture 110 or well inadvance.

When describing component amounts in the compositions described herein(e.g., the mixture 112 and pigmented polymer particles 124), a weightpercent based on the thermoplastic polymer 102 not inclusive of theinternal additive. For example, a composition comprising 1 wt % ofemulsion stabilizer by weight of 100 g of a thermoplastic polymer 102comprising 10 wt % internal additive and 90 wt % thermoplastic polymeris a composition comprising 0.9 g of emulsion stabilizer, 90 g ofthermoplastic polymer, and 10 g of internal additive.

The internal additive may be present in the thermoplastic polymer 102 atabout 0.1 wt % to about 60 wt % (or about 0.1 wt % to about 5 wt %, orabout 1 wt % to about 10 wt %, or about 5 wt % to about 20 wt %, orabout 10 wt % to about 30 wt %, or about 25 wt % to about 50 wt %, orabout 40 wt % to about 60 wt %) of the thermoplastic polymer 102. Forexample, the thermoplastic polymer 102 may comprise about 70 wt % toabout 85 wt % of a thermoplastic polymer and about 15 wt % to about 30wt % of an internal additive like glass fiber or carbon fiber.

Examples of internal additives include, but are not limited to, fillers,strengtheners, pigments, pH regulators, and the like, and combinationsthereof. Examples of fillers include, but are not limited to, glassfibers, glass particles, mineral fibers, carbon fiber, oxide particles(e.g., titanium dioxide and zirconium dioxide), metal particles (e.g.,aluminum powder), and the like, and any combination thereof. Examples ofpigments include, but are not limited to, organic pigments, inorganicpigments, carbon black, and the like, and any combination thereof.

The thermoplastic polymer 102 may be present in the mixture 112 at about5 wt % to about 60 wt % (or about 5 wt % to about 25 wt %, or about 10wt % to about 30 wt %, or about 20 wt % to about 45 wt %, or about 25 wt% to about 50 wt %, or about 40 wt % to about 60 wt %) of thethermoplastic polymer 102 and carrier fluid 104 combined.

Suitable carrier fluids 104 have a viscosity at 25° C. of about 1,000cSt to about 150,000 cSt (or about 1,000 cSt to about 60,000 cSt, orabout 40,000 cSt to about 100,000 cSt, or about 75,000 cSt to about150,000 cSt).

Examples of carrier fluids 104 include, but are not limited to, siliconeoil, fluorinated silicone oils, perfluorinated silicone oils,polyethylene glycols, alkyl-terminal polyethylene glycols (e.g., C1-C4terminal alkyl groups like tetraethylene glycol dimethyl ether (TDG)),paraffins, liquid petroleum jelly, vison oils, turtle oils, soya beanoils, perhydrosqualene, sweet almond oils, calophyllum oils, palm oils,parleam oils, grapeseed oils, sesame oils, maize oils, rapeseed oils,sunflower oils, cottonseed oils, apricot oils, castor oils, avocadooils, jojoba oils, olive oils, cereal germ oils, esters of lanolic acid,esters of oleic acid, esters of lauric acid, esters of stearic acid,fatty esters, higher fatty acids, fatty alcohols, polysiloxanes modifiedwith fatty acids, polysiloxanes modified with fatty alcohols,polysiloxanes modified with polyoxy alkylenes, and the like, and anycombination thereof. Examples of silicone oils include, but are notlimited to, polydimethylsiloxane (PDMS), methylphenylpolysiloxane, analkyl modified polydimethylsiloxane, an alkyl modifiedmethylphenylpolysiloxane, an amino modified polydimethylsiloxane, anamino modified methylphenylpolysiloxane, a fluorine modifiedpolydimethylsiloxane, a fluorine modified methylphenylpolysiloxane, apolyether modified polydimethylsiloxane, a polyether modifiedmethylphenylpolysiloxane, and the like, and any combination thereof.When the carrier fluid 104 comprises two or more of the foregoing, thecarrier fluid 104 may have one or more phases. For example,polysiloxanes modified with fatty acids and polysiloxanes modified withfatty alcohols (preferably with similar chain lengths for the fattyacids and fatty alcohols) may form a single-phase carrier fluid 104. Inanother example, a carrier fluid 104 comprising a silicone oil and analkyl-terminal polyethylene glycol may form a two-phase carrier fluid104.

The carrier fluid 104 may be present in the mixture 112 at about 40 wt %to about 95 wt % (or about 75 wt % to about 95 wt %, or about 70 wt % toabout 90 wt %, or about 55 wt % to about 80 wt %, or about 50 wt % toabout 75 wt %, or about 40 wt % to about 60 wt %) of the thermoplasticpolymer 102 and carrier fluid 104 combined.

In some instances, the carrier fluid 104 may have a density of about 0.6g/cm³ to about 1.5 g/cm³, and the thermoplastic polymer 102 has adensity of about 0.7 g/cm³ to about 1.7 g/cm³, wherein the thermoplasticpolymer has a density similar, lower, or higher than the density of thecarrier fluid.

Pigment 108 should be sufficiently stable to not decompose at theprocessing 114 temperatures. Pigments may impart a color, a metalliccolor, a pearlescent color, and/or a phosphorescent color particles.Examples of metallic and/or phosphorescent pigments include, but are notlimited to, synthetic mica (e.g., fluorphlogopite), natural mica (e.g.,muscovite), talc, sericite, kaolin, glass, SiO₂ flakes, Al₂O₃ flakes,glass flakes, acicular pigments (e.g., BiOCl, colored glass fibers,α-Fe₂O₃, and α-FeOOH), CaSO₄, iron oxides, chromium oxides, carbonblack, metal effect pigments (e.g., Al flakes and bronzes), opticallyvariable pigments (OVPs), liquid crystal polymer pigments (LCPs),holographic pigments, titanium dioxide, titanium suboxides, titaniumoxynitrides, Al₂O₃, Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO, zirconiumoxide, iron titanium oxides (iron titanates), other metal oxides, andthe like, and any combination thereof. Examples of phosphorescentpigments include, but are not limited to, zinc sulfide-based pigments(e.g., zinc sulfide doped with copper and/or manganese); strontiumaluminate-based pigments (e.g., SrAl₂O₄ doped with Eu and Dy, Sr₄Al₁₄O₂₅doped with Eu and Dy); strontium silicate-based pigments (e.g.,Sr₂MgSi₂O₇ doped with Dy and Eu, commercially available as P170 SPS BLUEfrom USR Optonix Inc); cadmium sulfide-based pigments; phosphoroussilicate-based pigments; phosphorous aluminate-based pigments; calciumsilicate-based pigments; calcium aluminate-based pigments (e.g., CaAl₂O₄doped with Eu and Nd); titanium aluminate-based pigment; titanium-basedaluminosilicate-based pigments; magnesium aluminate-based pigments;barium aluminate-based pigments; and the like; and any combinationthereof.

Examples of commercially available surface treated metallic and/orphosphorescent pigments include, but are not limited to, REFLEX™pigments (synthetic mica-based pearlescent pigments, available fromCQV), IRIODIN™ (mica-based, metal oxide-coated pearlescent pigments,available from Merck) (e.g., IRIODIN™ 300 “Gold Pearl” and IRIODIN™ 100“Silver Pearl”), SUNGEM™ (glass platelet-based pigments, available fromSun Chemical), SUNMICA™ (mica-based pigments, available from SunChemical), SYNCRYSTAL™ (metal oxide coated synthetic fluorphlogopiteflakes, available from Eckart), and the like, and any combinationthereof. Other metallic color pearlescent pigments from Merck includeTIMIRON® Bronze MP60 with a D50 volume average particle size (50% of thepigments have a volume size of less than the stated size) of 22-37microns, TIMIRON® Copper MP-65 D50 size of 22-37 microns, COLORONA®Oriental Beige D50 size of 3-10 microns, COLORONA® Aborigine Amber D50size of 18-25 microns, COLORONA® Passion Orange with D50 size of 18-25microns, COLORONA® Bronze Fine of D50 size of 7-14, COLORONA® Bronzewith D50 size of 18-25 microns, COLORONA® Bronze Sparkle of D50 size of28-42 microns, COLORONA® Copper Fine with D50 size of 7-14 microns,COLORONA® Copper with D50 size of 18-25, COLORONA® Copper Sparkle withD50 size of 25-39 microns, COLORONA® Red Brown with D50 size of 18-25microns, COLORONA® Russet with D50 size of 18-25 microns, COLORONA®Tibetan Ochre with D50 size of 18-25 microns, COLORONA® Sienna Fine withD50 size of 7-14 microns, COLORONA® Sienna with D50 size of 18-25microns, COLORONA® Bordeaux with D50 size of 18-25 microns, COLORONA®Glitter Bordeaux, COLORONA® Chameleon with D50 size of 18-25 microns.Also suitable are Merck mica based pigments with metal oxide particlecoatings such as the Merck silvery white pigments including TIMIRON®Super Silk MP-1005 with D50 size of 3-10 microns, TIMIRON® Super SheenMP-1001 with D50 size of 7-14 microns, TIMIRON® Super Silver Fine withD50 size of 9-13 microns, TIMIRON® Pearl Sheen MP-30 with D50 size of15-21 microns, TIMIRON® Satin MP-11171 with D50 size of 11-20 microns,TIMIRON® Ultra Luster MP-111 with D50 size of 18-25 microns, TIMIRON®Star Luster MP-111 with D50 size of 18-25 microns, TIMIRON® Pearl FlakeMP-10 with D50 size of 22-37 microns, TIMIRON® Super Silver with D50size of 17-26 microns, TIMIRON® Sparkle MP-47 with D50 size of 28-38microns, TIMIRON® Arctic Silver with D50 size of 19-25 microns, XIRONA®Silver with D50 size of 15-22 microns, RONASTAR® Silver with D50 size of25-45 microns, and the like, and any combination thereof. For verybright colors, examples from Merck include COLORONA® Carmine Red withD50 size of 10-60 microns giving a Red lustrous effect, COLORONA®Magenta with D50 size of 18-25 microns, giving a pink-violet lustrouseffect, COLORONA® Light Blue with D50 size of 18-25 microns, to give alight blue lustrous effect, COLORONA® Dark Blue with D50 size of 18-25microns to give a dark blue lustrous effect, COLORONA® Majestic Greenwith 18-25 microns to give a green lustrous color, COLORONA® BrilliantGreen of D5 19-26 microns to give a Green-golden lustrous color,COLORONA® Egyptian Emerald of D50 18-25 microns to give a dark greenlustrous effect, COLORONA® Patagonian Purple of 18-25 microns size togive a purple lustrous effect, and the like, and any combinationthereof. Mica based special effect pigments having a D50 from about 18microns to about 50 microns from Eckart may also be used, such asDORADO® PX 4001, DORADO® PX 4261, DORADO® PX 4271, DORADO® PX 4310,DORADO® PX 4331, DORADO® PX 4542, PHOENIX® XT, PHOENIX® XT 2001,PHOENIX® XT 3001, PHOENIX® XT 4001, PHOENIX® XT 5001, PHOENIX® PX 1000,PHOENIX® PX 1001, PHOENIX® PX 1221, PHOENIX® PX 1231, PHOENIX® PX 1241,PHOENIX® PX 1251, PHOENIX® PX 1261, PHOENIX® PX 1271, PHOENIX® PX 1310,PHOENIX® PX 1320, PHOENIX® PX 1502, PHOENIX® PX 1522, PHOENIX® PX 1542,PHOENIX® PX 2000, PHOENIX® PX 2000 L, PHOENIX® PX 2001, PHOENIX® PX2011, PHOENIX® PX 2021, PHOENIX® PX 2221, PHOENIX® PX 2231, PHOENIX® PX2241, PHOENIX® PX 2251, PHOENIX® PX 2261, PHOENIX® PX 2271, PHOENIX® PX3001, PHOENIX® PX 4000, PHOENIX® PX 4001, PHOENIX® PX 4221, PHOENIX® PX4231, PHOENIX® PX 4241, PHOENIX® PX 4251, PHOENIX® PX 4261, PHOENIX® PX4271, PHOENIX® PX 4310, PHOENIX® PX 4320, PHOENIX® PX 4502, PHOENIX® PX4522, PHOENIX® PX 4542, PHOENIX® PX 5000, PHOENIX® PX 5001, PHOENIX® PX5310, PHOENIX® PX 5331, and the like, and any combination thereof.Special effect pigments such as Silberline aluminum flake pigments maybe used, such as 16 micron DF-1667, 55 micron DF-2750, 27 micronDF-3500, 35 micron DF-3622, 15 micron DF-554, 20 micron DF-L-520AR, 20micron LED-1708AR, 13 micron LED-2314AR, 55 micron SILBERCOTE™ PC 0452Z,47 micron SILBERCOTE™ PC 1291X, 36 micron SILBERCOTE™, 36 micronSILBERCOTE™ PC 3331X, 31 micron SILBERCOTE™ PC 4352Z, 33 micronSILBERCOTE™ PC 4852X, 20 micron SILBERCOTE™ PC 6222X, 27 micronSILBERCOTE™ PC 6352Z, 25 micron SILBERCOTE™ PC 6802X, 14 micronSILBERCOTE™ PC 8152Z, 14 micron SILBERCOTE™ PC 8153X, 16 micronSILBERCOTE™ PC 8602X, 20 micron SILVET®/SILVEX® 890 Series, 16 micronSILVET®/SILVEX® 950 Series, and the like, and any combination thereof.

Pigments may have an average diameter (or D50) of about 1 micron toabout 500 microns (or about 1 micron to about 25 microns, or about 5microns to about 50 microns, or about 25 microns to about 200 microns,or about 100 microns to about 300 microns, or about 250 microns to about500 microns).

The pigmented polymer particles of the present disclosure may includethe pigment (or cumulative pigments if more than one is used) at about0.01 wt % to about 30 wt % (or about 0.01 wt % to about 1 wt %, or about0.1 wt % to about 5 wt %, or about 1 wt % to about 10 wt %, or about 5wt % to about 20 wt %, or about 10 wt % to about 30 wt %) of thethermoplastic polymer 102.

The pigmented polymer particles may comprise one or more pigments. Thecomposition and concentration of the pigments may be used foridentifying objects, tracking objects, authenticating objects, and/ordetermining the health of objects made from the pigmented polymerparticles. That is, the pigments may be used as a fingerprint foridentifying objects, tracking objects, and/or authenticating objects.Further or alternatively, the pigments may be used as an indicator for aportion of the object as a way of identifying defects (e.g., cracks orwear) and/or the extent of such defects.

The emulsion stabilizers used in the methods and compositions of thepresent disclosure may comprise nanoparticles (e.g. oxide nanoparticles,carbon black, polymer nanoparticles, and combinations thereof),surfactants, and the like, and any combination thereof.

Oxide nanoparticles may be metal oxide nanoparticles, non-metal oxidenanoparticles, or mixtures thereof. Examples of oxide nanoparticlesinclude, but are not limited to, silica, titania, zirconia, alumina,iron oxide, copper oxide, tin oxide, boron oxide, cerium oxide, thalliumoxide, tungsten oxide, and the like, and any combination thereof. Mixedmetal oxides and/or non-metal oxides, like aluminosilicates,borosilicates, and aluminoborosilicates, are also inclusive in the termmetal oxide. The oxide nanoparticles may by hydrophilic or hydrophobic,which may be native to the particle or a result of surface treatment ofthe particle. For example, a silica nanoparticle having a hydrophobicsurface treatment, like dimethyl silyl, trimethyl silyl, and the like,may be used in methods and compositions of the present disclosure.Additionally, silica with functional surface treatments likemethacrylate functionalities may be used in methods and compositions ofthe present disclosure. Unfunctionalized oxide nanoparticles may also besuitable for use as well.

Commercially available examples of silica nanoparticles include, but arenot limited to, AEROSIL® particles available from Evonik (e.g., AEROSIL®R812S (about 7 nm average diameter silica nanoparticles having ahydrophobically modified surface and a BET surface area of 260±30 m²/g),AEROSIL® RX50 (about 40 nm average diameter silica nanoparticles havinga hydrophobically modified surface and a BET surface area of 35±10m²/g), AEROSIL® 380 (silica nanoparticles having a hydrophilicallymodified surface and a BET surface area of 380±30 m²/g), and the like,and any combination thereof.

Carbon black is another type of nanoparticle that may be present as anemulsion stabilizer in the compositions and methods disclosed herein.Various grades of carbon black will be familiar to one having ordinaryskill in the art, any of which may be used herein. Other nanoparticlescapable of absorbing infrared radiation may be used similarly.

Polymer nanoparticles are another type of nanoparticle that may bepresent as an emulsion stabilizer in the disclosure herein. Suitablepolymer nanoparticles may include one or more polymers that arethermosetting and/or crosslinked, such that they do not melt whenprocessed by melt emulsification according to the disclosure herein.High molecular weight thermoplastic polymers having high melting ordecomposition points may similarly comprise suitable polymernanoparticle emulsion stabilizers.

The nanoparticles may have an average diameter (D50 based on volume) ofabout 1 nm to about 500 nm (or about 10 nm to about 150 nm, or about 25nm to about 100 nm, or about 100 nm to about 250 nm, or about 250 nm toabout 500 nm).

The nanoparticles may have a BET surface area of about 10 m²/g to about500 m²/g (or about 10 m²/g to about 150 m²/g, or about 25 m²/g to about100 m²/g, or about 100 m²/g to about 250 m²/g, or about 250 m²/g toabout 500 m²/g).

Nanoparticles may be included in the mixture 112 at a concentration ofabout 0.01 wt % to about 10 wt % (or about 0.01 wt % to about 1 wt %, orabout 0.1 wt % to about 3 wt %, or about 1 wt % to about 5 wt %, orabout 5 wt % to about 10 wt %) based on the weight of the thermoplasticpolymer 102.

Surfactants may be anionic, cationic, nonionic, or zwitterionic.Examples of surfactants include, but are not limited to, sodium dodecylsulfate, sorbitan oleates,poly[dimethylsiloxane-co-[3-(2-(2-hydroxyethoxy)ethoxy)propylmethylsiloxane],docusate sodium (sodium1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate), and the like, andany combination thereof. Commercially available examples of surfactantsinclude, but are not limited to, CALFAX® DB-45 (sodium dodecyl diphenyloxide disulfonate, available from Pilot Chemicals), SPAN® 80 (sorbitanmaleate non-ionic surfactant), MERPOL® surfactants (available fromStepan Company), TERGITOL™ TMN-6 (a water-soluble, nonionic surfactant,available from DOW), TRITON™ X-100 (octyl phenol ethoxylate, availablefrom SigmaAldrich), IGEPAL® CA-520 (polyoxyethylene (5) isooctylphenylether, available from SigmaAldrich), BRIJ® S10 (polyethylene glycoloctadecyl ether, available from SigmaAldrich), and the like, and anycombination thereof.

Surfactants may be included in the mixture 112 at a concentration ofabout 0.01 wt % to about 10 wt % (or about 0.01 wt % to about 1 wt %, orabout 0.5 wt % to about 2 wt %, or about 1 wt % to about 3 wt %, orabout 2 wt % to about 5 wt %, or about 5 wt % to about 10 wt %) based onthe weight of the polyamide 102. Alternatively, the mixture 112 maycomprise no (or be absent of) surfactant.

A weight ratio of nanoparticles to surfactant may be about 1:10 to about10:1 (or about 1:10 to about 1:1, or about 1:5 to about 5:1, or about1:1 to about 10:1).

As described above, the components 102, 104, and 106 can be added in anyorder and include mixing and/or heating during the process of combining110 the components 102, 104, and 106. For example, the emulsionstabilizer 106 may first be dispersed in the carrier fluid 104,optionally with heating said dispersion, before adding the thermoplasticpolymer 102. In another nonlimiting example, the thermoplastic polymer102 may be heated to produce a polymer melt to which the carrier fluid104 and emulsion stabilizer 106 are added together or in either order.In yet another nonlimiting example, the thermoplastic polymer 102 andcarrier fluid 104 can be mixed at a temperature greater than the meltingpoint or softening temperature of the thermoplastic polymer 102 and at ashear rate sufficient enough to disperse the thermoplastic polymer meltin the carrier fluid 104. Then, the emulsion stabilizer 106 can be addedto form the mixture 112 and maintained at suitable process conditionsfor a set period of time.

Combining 110 the components 102, 104, and 106 in any combination canoccur in a mixing apparatus used for the processing 114 and/or anothersuitable vessel. By way of nonlimiting example, the thermoplasticpolymer 102 may be heated to a temperature greater than the meltingpoint or softening temperature of the thermoplastic polymer 102 in themixing apparatus used for the processing 114, and the emulsionstabilizer 106 may be dispersed in the carrier fluid 104 in anothervessel. Then, said dispersion may be added to the melt of thethermoplastic polymer 102 in the mixing apparatus used for theprocessing 114.

The mixing apparatuses used for the processing 114 to produce the meltemulsion 116 should be capable of maintaining the melt emulsion 116 at atemperature greater than the melting point or softening temperature ofthe thermoplastic polymer 102 and applying a shear rate sufficient todisperse the polymer melt in the carrier fluid 104 as droplets.

Examples of mixing apparatuses used for the processing 114 to producethe melt emulsion 116 include, but are not limited to, extruders (e.g.,continuous extruders, batch extruders, and the like), stirred reactors,blenders, reactors with inline homogenizer systems, and the like, andapparatuses derived therefrom.

Processing 114 and forming the melt emulsion 116 at suitable processconditions (e.g., temperature, shear rate, and the like) for a setperiod of time.

The temperature of processing 114 and forming the melt emulsion 116should be a temperature greater than the melting point or softeningtemperature of the thermoplastic polymer 102 and less than thedecomposition temperature of any components 102, 104, and 106 in themixture 112. For example, the temperature of processing 114 and formingthe melt emulsion 116 may be about 1° C. to about 50° C. (or about 1° C.to about 25° C., or about 5° C. to about 30° C., or about 20° C. toabout 50° C.) greater than the melting point or softening temperature ofthe thermoplastic polymer 102 provided the temperature of processing 114and forming the melt emulsion 116 is less than the decompositiontemperature of any components 102, 104, and 106 in the mixture 112.

The shear rate of processing 114 and forming the melt emulsion 116should be sufficiently high to disperse the polymer melt in the carrierfluid 104 as droplets. Said droplets should comprise droplets having adiameter of about 1000 μm or less (or about 1 μm to about 1000 μm, orabout 1 μm to about 50 μm, or about 10 μm to about 100 μm, or about 10μm to about 250 μm, or about 50 μm to about 500 μm, or about 250 μm toabout 750 μm, or about 500 μm to about 1000 μm).

The time for maintaining said temperature and shear rate for processing114 and forming the melt emulsion 116 may be 10 seconds to 18 hours orlonger (or 10 seconds to 30 minutes, or 5 minutes to 1 hour, or 15minutes to 2 hours, or 1 hour to 6 hours, or 3 hours to 18 hours).Without being limited by theory, it is believed that a steady state ofdroplet sizes will be reached at which point processing 114 can bestopped. That time may depend on, among other things, the temperature,shear rate, thermoplastic polymer 102 composition, the carrier fluid 104composition, and the emulsion stabilizer 106 composition.

The melt emulsion 116 may then be cooled 118. Cooling 118 can be slow(e.g., allowing the melt emulsion to cool under ambient conditions) tofast (e.g., quenching). For example, the rate of cooling may range fromabout 10° C./hour to about 100° C./second to almost instantaneous withquenching (for example in dry ice) (or about 10° C./hour to about 60°C./hour, or about 0.5° C./minute to about 20° C./minute, or about 1°C./minute to about 5° C./minute, or about 10° C./minute to about 60°C./minute, or about 0.5° C./second to about 10° C./second, or about 10°C./second to about 100° C./second).

During cooling, little to no shear may be applied to the melt emulsion116. In some instances, the shear applied during heating may be appliedduring cooling.

The cooled mixture 120 resulting from cooling 118 the melt emulsion 116comprises solidified pigmented polymer particles 124 and othercomponents 126 (e.g., the carrier fluid 104, excess emulsion stabilizer106, and the like). The thermoplastic polymer particles may be dispersedin the carrier fluid or settled in the carrier fluid.

The cooled mixture 120 may then be treated 122 to the separate pigmentedpolymer particles 124 from the other components 126. Suitable treatmentsinclude, but are not limited to, washing, filtering, centrifuging,decanting, and the like, and any combination thereof.

Solvents used for washing the pigmented polymer particles 124 shouldgenerally be (a) miscible with the carrier fluid 104 and (b) nonreactive(e.g., non-swelling and non-dissolving) with the thermoplastic polymer102. The choice of solvent will depend on, among other things, thecomposition of the carrier fluid and the composition of thethermoplastic polymer 102.

Examples of solvents include, but are not limited to, hydrocarbonsolvents (e.g., pentane, hexane, heptane, octane, cyclohexane,cyclopentane, decane, dodecane, tridecane, and tetradecane), aromatichydrocarbon solvents (e.g., benzene, toluene, xylene, 2-methylnaphthalene, and cresol), ether solvents (e.g., diethyl ether,tetrahydrofuran, diisopropyl ether, and dioxane), ketone solvents (e.g.,acetone and methyl ethyl ketone), alcohol solvents (e.g., methanol,ethanol, isopropanol, and n-propanol), ester solvents (e.g., ethylacetate, methyl acetate, butyl acetate, butyl propionate, and butylbutyrate), halogenated solvents (e.g., chloroform, bromoform,1,2-dichloromethane, 1,2-dichloroethane, carbon tetrachloride,chlorobenzene, and hexafluoroisopropanol), water, and the like, and anycombination thereof.

Solvent may be removed from the pigmented polymer particles 124 bydrying using an appropriate method such as air-drying, heat-drying,reduced pressure drying, freeze drying, or a hybrid thereof. The heatingmay be performed preferably at a temperature lower than the glasstransition point of the thermoplastic polymer (e.g., about 50° C. toabout 150° C.).

Advantageously, carrier fluids and washing solvents of the systems andmethods described herein (e.g., method 100) can be recycled and reused.One skilled in the art will recognize any necessary cleaning of usedcarrier fluid and solvent necessary in the recycling process.

The pigmented polymer particles 124 after separation from the othercomponents 126 may optionally be further purified 128. For example, tonarrow the particle size distribution (or reduce the diameter span), thepigmented polymer particles 124 can be passed through a sieve having apore size of about 10 μm to about 250 μm (or about 10 μm to about 100μm, or about 50 μm to about 200 μm, or about 150 μm to about 250 μm).

In another example purification technique, the pigmented polymerparticles 124 may be washed with water to remove surfactant whilemaintaining substantially all of the nanoparticles associated with thesurface of the pigmented polymer particles 124. In yet another examplepurification technique, the pigmented polymer particles 124 may beblended with additives to achieve a desired final product. For clarity,because such additives are blended with the thermoplastic particles 124or other particles resultant from the methods described herein after theparticles are solidified, such additives are referred to herein as“external additives.” Examples of external additives include flow aids,other polymer particles, fillers, and the like, and any combinationthereof.

In some instances, a surfactant used in making the pigmented polymerparticles 124 may be unwanted in downstream applications. Accordingly,yet another example purification technique may include at leastsubstantial removal of the surfactant from the pigmented polymerparticles 124 (e.g., by washing and/or pyrolysis).

The pigmented polymer particles 124 and/or purified pigmented polymerparticles 130 (referred to as pigmented polymer particles 124/130) maybe characterized by composition, physical structure, and the like.

As described above, the emulsion stabilizers are at the interfacebetween the polymer melt and the carrier fluid. As a result, when themixture is cooled, the emulsion stabilizers remain at, or in thevicinity of, said interface. Therefore, the structure of the pigmentedpolymer particles 124/130 is, in general when emulsion stabilizers areused, includes emulsion stabilizers (a) dispersed on an outer surface ofthe pigmented polymer particles 124/130 and/or (b) embedded in an outerportion (e.g., outer 1 vol %) of the pigmented polymer particles124/130.

Further, where voids form inside the polymer melt droplets, emulsionstabilizers 106 should generally be at (and/or embedded in) theinterface between the interior of the void and the thermoplasticpolymer. The voids generally do not contain the thermoplastic polymer.Rather, the voids may contain, for example, carrier fluid, air, or bevoid. The pigmented polymer particles 124/130 may comprise carrier fluidat about 5 wt % or less (or about 0.001 wt % to about 5 wt %, or about0.001 wt % to about 0.1 wt %, or about 0.01 wt % to about 0.5 wt %, orabout 0.1 wt % to about 2 wt %, or about 1 wt % to about 5 wt %) of thepigmented polymer particles 124/130.

The thermoplastic polymer 102 may be present in the pigmented polymerparticles 124/130 at about 90 wt % to about 99.5 wt % (or about 90 wt %to about 95 wt %, or about 92 wt % to about 97 wt %, or about 95 wt % toabout 99.5 wt %) of the pigmented polymer particles 124/130.

When included, the emulsion stabilizers 106 may be present in thepigmented polymer particles 124/130 at about 10 wt % or less (or about0.01 wt % to about 10 wt %, or about 0.01 wt % to about 1 wt %, or about0.5 wt % to about 5 wt %, or about 3 wt % to about 7 wt %, or about 5 wt% to about 10 wt %) of the pigmented polymer particles 124/130. Whenpurified to at least substantially remove surfactant or another emulsionstabilizer, the emulsion stabilizers 106 may be present in the particles130/136 at less than 0.01 wt % (or 0 wt % to about 0.01 wt %, or 0 wt %to 0.001 wt %).

Upon forming thermoplastic particulates according to the disclosureherein using particulate emulsion stabilizers, at least a portion of theparticulate emulsion stabilizers, such as silica nanoparticles, may bedisposed as a coating upon the outer surface of the thermoplasticparticulates (and coated pigment, when produced). At least a portion ofthe surfactant, if used, may be associated with the outer surface aswell. The coating may be disposed substantially uniformly upon the outersurface. As used herein with respect to a coating, the term“substantially uniform” refers to even coating thickness in surfacelocations covered by the coating composition (e.g., nanoparticles and/orsurfactant), particularly the entirety of the outer surface. Theemulsion stabilizers 106 may form a coating that covers at least 5% (orabout 5% to about 100%, or about 5% to about 25%, or about 20% to about50%, or about 40% to about 70%, or about 50% to about 80%, or about 60%to about 90%, or about 70% to about 100%) of the surface area of thepigmented polymer particles 124/130 (and coated pigment, when produced).When purified to at least substantially remove surfactant or anotheremulsion stabilizer, the emulsion stabilizers 106 may be present in theparticles 130/136 at less than 25% (or 0% to about 25%, or about 0.1% toabout 5%, or about 0.1% to about 1%, or about 1% to about 5%, or about1% to about 10%, or about 5% to about 15%, or about 10% to about 25%) ofthe surface area of the particles 130/136. The coverage of the emulsionstabilizers 106 on an outer surface of the pigmented polymer particles124/130 may be determined using image analysis of the scanning electronmicroscope images (SEM micrographs). The emulsion stabilizers 106 mayform a coating that covers at least 5% (or about 5% to about 100%, orabout 5% to about 25%, or about 20% to about 50%, or about 40% to about70%, or about 50% to about 80%, or about 60% to about 90%, or about 70%to about 100%) of the surface area of the pigmented polymer particles124/130 (and coated pigment, when produced). When purified to at leastsubstantially remove surfactant or another emulsion stabilizer, theemulsion stabilizers 106 may be present in the particles 130/136 at lessthan 25% (or 0% to about 25%, or about 0.1% to about 5%, or about 0.1%to about 1%, or about 1% to about 5%, or about 1% to about 10%, or about5% to about 15%, or about 10% to about 25%) of the surface area of theparticles 130/136. The coverage of the emulsion stabilizers 106 on anouter surface of the pigmented polymer particles 124/130 may bedetermined using image analysis of the SEM micrographs

The pigmented polymer particles 124/130 may have a D10 of about 0.1 μmto about 125 μm (or about 0.1 μm to about 5 μm, about 1 μm to about 10μm, about 5 μm to about 30 μm, or about 1 μm to about 25 μm, or about 25μm to about 75 μm, or about 50 μm to about 85 μm, or about 75 μm toabout 125 μm), a D50 of about 0.5 μm to about 200 μm (or about 0.5 μm toabout 10 μm, or about 5 μm to about 50 μm, or about 30 μm to about 100μm, or about 30 μm to about 70 μm, or about 25 μm to about 50 μm, orabout 50 μm to about 100 μm, or about 75 μm to about 150 μm, or about100 μm to about 200 μm), and a D90 of about 3 μm to about 300 μm (orabout 3 μm to about 15 μm, or about 10 μm to about 50 μm, or about 25 μmto about 75 μm, or about 70 μm to about 200 μm, or about 60 μm to about150 μm, or about 150 μm to about 300 μm), wherein D10<D50<D900. Thepigmented polymer particles 124/130 may also have a diameter span ofabout 0.2 to about 10 (or about 0.2 to about 0.5, or about 0.4 to about0.8, or about 0.5 to about 1.0, or about 1 to about 3, or about 2 toabout 5, or about 5 to about 10). Without limitation, diameter spanvalues of 1.0 or greater are considered broad, and diameter spans valuesof 0.75 or less are considered narrow.

In a first nonlimiting example, the pigmented polymer particles 124/130may have a D10 of about 0.1 μm to about 10 μm, a D50 of about 0.5 μm toabout 25 μm, and a D90 of about 3 μm to about 50 μm, whereinD10<D50<D90. Said pigmented polymer particles 124/130 may have adiameter span of about 0.2 to about 2.

In a second nonlimiting example, the pigmented polymer particles 124/130may have a D10 of about 5 μm to about 30 μm, a D50 of about 30 μm toabout 70 μm, and a D90 of about 70 μm to about 120 μm, whereinD10<D50<D90. Said pigmented polymer particles 124/130 may have adiameter span of about 1.0 to about 2.5.

In a third nonlimiting example, the pigmented polymer particles 124/130may have a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm toabout 110 μm, and a D90 of about 110 μm to about 175 μm, whereinD10<D50<D90. Said pigmented polymer particles 124/130 may have adiameter span of about 0.6 to about 1.5.

In a fourth nonlimiting example, the pigmented polymer particles 124/130may have a D10 of about 75 μm to about 125 μm, a D50 of about 100 μm toabout 200 μm, and a D90 of about 125 μm to about 300 μm, whereinD10<D50<D90. Said pigmented polymer particles 124/130 may have adiameter span of about 0.2 to about 1.2.

In a fifth nonlimiting example, the pigmented polymer particles 124/130may have a D10 of about 1 μm to about 50 μm (or about 5 μm to about 30μm, or about 1 μm to about 25 μm, or about 25 μm to about 50 μm), a D50of about 25 μm to about 100 μm (or about 30 μm to about 100 μm, or about30 μm to about 70 μm, or about 25 μm to about 50 μm, or about 50 μm toabout 100 μm), and a D90 of about 60 μm to about 300 μm (or about 70 μmto about 200 μm, or about 60 μm to about 150 μm, or about 150 μm toabout 300 μm), wherein D10<D50<D90. The pigmented polymer particles124/130 may also have a diameter span of about 0.4 to about 3 (or about0.6 to about 2, or about 0.4 to about 1.5, or about 1 to about 3).

The pigmented polymer particles 124/130 may have a circularity of about0.9 or greater (or about 0.90 to about 1.0, or about 0.93 to about 0.99,or about 0.95 to about 0.99, or about 0.97 to about 0.99, or about 0.98to 1.0).

The pigmented polymer particles 124/130 may have an angle of repose ofabout 25° to about 45° (or about 25° to about 35°, or about 30° to about40°, or about 35° to about 45°).

The pigmented polymer particles 124/130 may have a Hausner ratio ofabout 1.0 to about 1.5 (or about 1.0 to about 1.2, or about 1.1 to about1.3, or about 1.2 to about 1.35, or about 1.3 to about 1.5).

The pigmented polymer particles 124/130 may have a bulk density of about0.3 g/cm³ to about 0.8 g/cm³ (or about 0.3 g/cm³ to about 0.6 g/cm³, orabout 0.4 g/cm³ to about 0.7 g/cm³, or about 0.5 g/cm³ to about 0.6g/cm³, or about 0.5 g/cm³ to about 0.8 g/cm³).

Depending on the temperature and shear rate of processing 114 and thecomposition and relative concentrations of the components 102, 104, and106, different shapes of the structures that compose the pigmentedpolymer particles 124/130 have been observed. Typically, the pigmentedpolymer particles 124/130 comprise substantially spherical particles(having a circularity of about 0.97 or greater). However, otherstructures including disc and elongated structures have been observed inthe pigmented polymer particles 124/130. Therefore, the pigmentedpolymer particles 124/130 may comprise one or more of: (a) substantiallyspherical particles having a circularity of 0.97 or greater, (b) discstructures having an aspect ratio of about 2 to about 10, and (c)elongated structures having an aspect ratio of 10 or greater. Each ofthe (a), (b), and (c) structures have emulsion stabilizers dispersed onan outer surface of the (a), (b), and (c) structures and/or embedded inan outer portion of the (a), (b), and (c) structures. At least some ofthe (a), (b), and (c) structures may be agglomerated. For example, the(c) elongated structures may be laying on the surface of the (a)substantially spherical particles.

The pigmented polymer particles 124/130 may have a sintering window thatis within 10° C., preferably within 5° C., of the sintering window ofthe thermoplastic polymer.

Applications of Pigmented Polymer Particles

The pigmented polymer particles described herein may be used to producea variety of articles. By way of nonlimiting example, 3-D printingprocesses of the present disclosure may comprise: depositing pigmentedpolymer particles described herein upon a surface (e.g., in layersand/or in a specified shape), and once deposited, heating at least aportion of the particles to promote consolidation thereof and form aconsolidated body (or object). The consolidated body may have a voidpercentage of about 5% or less (e.g., 0% to about 5%, or about 0.5% toabout 2%, or about 1% to about 3%, or about 2% to about 5%) after beingconsolidated. For example, heating and consolidation of thethermoplastic polymer particles may take place in a 3-D printingapparatus employing a laser, such that heating and consolidation takeplace by selective laser sintering.

Examples of articles that may be produced by such methods where thepigmented polymer particles may be used to form all or a portion of saidarticles include, but are not limited to, particles, films, packaging,toys, household goods, automotive parts, aerospace/aircraft-relatedparts, containers (e.g., for food, beverages, cosmetics, personal carecompositions, medicine, and the like), shoe soles, furniture parts,decorative home goods, plastic gears, screws, nuts, bolts, cable ties,jewelry, art, sculpture, medical items, prosthetics, orthopedicimplants, production of artifacts that aid learning in education, 3Danatomy models to aid in surgeries, robotics, biomedical devices(orthotics), home appliances, dentistry, electronics, sporting goods,and the like. Further, particles may be useful in applications thatinclude, but are not limited to, paints, powder coatings, ink jetmaterials, electrophotographic toners, 3D printing, and the like.

In addition to the pigmented polymer particles described herein may havea specific fingerprint (e.g., color spectrum, phosphorescence, and thelike, and any combination thereof) that is useful in identifyingobjects, tracking objects, authenticating objects, and/or determiningthe health of objects. Further, the placement of where the pigmentedpolymer particles or the portion(s) of the object formed therefrom arelocated in the objects as another layer of fingerprinting the objectsfor identifying objects, tracking objects, authenticating objects,and/or determining the health of objects.

Methods of identifying objects, tracking objects, authenticatingobjects, and/or determining the health of objects may include (a)exposing the object comprising or produced from the pigmented polymerparticles to an exciting cause (e.g., broad spectrum light, ultravioletwavelength lights of light, a specific wavelength of light, or thelike); (b) sensing one or more spectra related to color and/orphosphorescence; and (c) comparing the spectra to the known spectra forthe pigments used in said object or portion thereof. Optionally, thelocation of where the spectra area is located on the object may becompared to the known location where the spectra area should be. Thecomparison(s) can be used for identifying and/or authenticating theobject. For tracking, the comparison(s) may be done and/or the detectedspectra and/or spectra area may be logged into a database along with thephysical location of the object. Further, the health of objects thatwear and/or crack can be ascertained. For example, a core portion of thearticle may comprise or be formed from the pigmented polymer particlesand an outer portion may cover the core portion and not comprise or beformed from the pigmented polymer particles. Then, the appearance ofcolor and/or phosphorescence may indicate that the object is at or nearthe end of life.

Example Embodiments

A first nonlimiting example embodiment is a composition comprising:pigmented polymer particles comprising a thermoplastic polymer and apigment (e.g., colored pigment, metallic pigment, pearlescent pigment,phosphorescent pigment, or any combination thereof) having amelt-emulsified morphology. The first nonlimiting example embodiment mayinclude one or more of: Element 1: wherein the melt-emulsifiedmorphology comprises the pigment has a coating comprising thethermoplastic polymer and the coated pigment adhered to a thermoplasticpolymer particle; Element 2: Element 1 and wherein the coating has anemulsion stabilizer coating (e.g., the emulsion stabilizer may beembedded in the coating of the pigment); Element 3: wherein the pigmentis embedded in an outer surface of a thermoplastic polymer particle;Element 4: wherein the pigment is encapsulated by a thermoplasticpolymer particle; Element 5: the composition further comprising thepigment having a coating and not being adhered to, embedded in, orencapsulated by a thermoplastic polymer particle; Element 6: Element 5and wherein the coating of the pigment has an emulsion stabilizercoating (e.g., the emulsion stabilizer may be embedded in the coating ofthe pigment); Element 7: wherein the pigmented polymer particles have aD10 of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200μm, and a D90 of about 3 μm to about 300 μm, wherein D10<D50<D90;Element 8: wherein the pigmented polymer particles have a diameter spanof about 0.2 to about 10; Element 9: wherein the pigmented polymerparticles have a Hausner ratio of about 1.0 to about 1.5; Element 10:wherein the pigmented polymer particles have an emulsion stabilizercoating; Element 11: Element 10 and wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles, and wherein at least someof the emulsion stabilizer is embedded in the outer surface of thepigmented polymer particles; Element 12: Element 10 and wherein at leastsome of the pigmented polymer particles have a void comprising theemulsion stabilizer at a void/polymer interface; Element 13: Element 12and wherein the emulsion stabilizer comprises nanoparticles and thenanoparticles are embedded in the void/polymer interface; and Element14: Element 12 and wherein the void contains the carrier fluid. Examplesof combinations include, but are not limited to, Element 1 (optionallyin combination with Element 2) in combination with one or more ofElements 3-14; Element 3 in combination with one or more of Elements4-14; Element 4 in combination with one or more of Elements 5-14;Element 5 (optionally in combination with Element 6) in combination withone or more of Elements 7-14; Element 7 in combination with one or moreof Elements 8-14; Element 8 in combination with one or more of Elements9-14; Element 9 in combination with one or more of Elements 10-14;Element 10 in combination with Element 11 and/or 12 and, when incombination with Element 12 optionally in further combination withElement 13 and/or 14; and two or more of Element 1 (optionally incombination with Element 2), Element 3, Element 4, and Element 5 incombination (optionally in combination with Element 6).

A second nonlimiting example embodiment is a composition comprising:pigmented polymer particles comprising a thermoplastic polymer and apigment (e.g., colored pigment, metallic pigment, pearlescent pigment,phosphorescent pigment, or any combination thereof) wherein at leastsome of the pigmented polymer particles have a morphology according to(a), (b), (c), or any combination thereof: (a) the pigment having acoating comprising the thermoplastic polymer and the coated pigmentadhered to a thermoplastic polymer particle, (b) the pigment beingembedded in an outer surface of the thermoplastic polymer particle, and(c) the pigment being encapsulated by the thermoplastic polymerparticle. The second nonlimiting example embodiment may include one ormore of: Element 2; Element 5; Element 6; Element 7; Element 8; Element9; Element 10; Element 11; Element 12; Element 13; and Element 14,including in any of the combinations per the first nonlimiting exampleembodiment.

A third nonlimiting example embodiment is a method comprising:depositing, upon a surface, the pigmented polymer particles of the firstor second nonlimiting example embodiment (optionally in combination withone or more of Elements 1-14) optionally in combination with otherthermoplastic polymer particles; and once deposited, heating at least aportion of the particles to promote consolidation thereof and form aconsolidated body.

A fourth nonlimiting example embodiment is a method comprising: mixing amixture comprising a thermoplastic polymer, a carrier fluid that isimmiscible with the thermoplastic polymer, a pigment (e.g., coloredpigment, metallic pigment, pearlescent pigment, phosphorescent pigment,or any combination thereof), and optionally an emulsion stabilizer at atemperature greater than a melting point or softening temperature of thethermoplastic polymer and at a shear rate sufficiently high to dispersethe thermoplastic polymer in the carrier fluid; cooling the mixture tobelow the melting point or softening temperature of the thermoplasticpolymer to form pigmented polymer particles comprising a thermoplasticpolymer and a pigment having a melt-emulsified morphology; andseparating the pigmented polymer particles from the carrier fluid.

A fifth nonlimiting example embodiment is a method comprising: mixing amixture comprising a thermoplastic polymer, a carrier fluid that isimmiscible with the thermoplastic polymer, a pigment (e.g., coloredpigment, metallic pigment, pearlescent pigment, phosphorescent pigment,or any combination thereof), and optionally an emulsion stabilizer at atemperature greater than a melting point or softening temperature of thethermoplastic polymer and at a shear rate sufficiently high to dispersethe thermoplastic polymer in the carrier fluid; cooling the mixture tobelow the melting point or softening temperature of the thermoplasticpolymer to form pigmented polymer particles comprising a thermoplasticpolymer and a pigment, wherein at least some of the pigmented polymerparticles have a morphology according to (a), (b), (c), or anycombination thereof: (a) the pigment having a coating comprising thethermoplastic polymer and the coated pigment adhered to a thermoplasticpolymer particle, (b) the pigment being embedded in an outer surface ofthe thermoplastic polymer particle, and (c) the pigment beingencapsulated by the thermoplastic polymer particle; and separating thepigmented polymer particles from the carrier fluid.

The fourth or fifth nonlimiting example embodiment may include one ormore of: Element 1; Element 2; Element 3; Element 4; Element 5; Element6; Element 7; Element 8; Element 9; Element 15: wherein the pigment is afirst pigment, and wherein the mixture further comprises a secondpigment different than the first pigment; Element 16: wherein thepigmented polymer particles comprise 0.01 wt % to 30 wt % of the pigmentbased on the weight of the thermoplastic polymer in the pigmentedpolymer particles; Element 17: wherein the emulsion stabilizer isincluded in the mixture, and wherein the emulsion stabilizer coats atleast a portion of an outer surface of the pigmented polymer particles;and Element 18: Element 17 and wherein the emulsion stabilizer isembedded in the outer surface. Examples of combinations include, but arenot limited to, two or more of Element 1 (optionally in combination withElement 2), Element 3, Element 4, and Element 5 in combination(optionally in combination with Element 6); one or more of Element 1-6in combination with one or more of Elements 7-9 and 15-18; Element 7 incombination with one or more of Elements 8-9 and 15-18; Element 8 incombination with one or more of Elements 9 and 15-18; Element 9 incombination with one or more of Elements 15-18; Element 15 incombination with one or more of Elements 16-18; and two or more ofElements 16-18 in combination.

Clauses

Clause 1. A composition comprising: pigmented polymer particlescomprising a thermoplastic polymer and a pigment (e.g., colored pigment,metallic pigment, pearlescent pigment, phosphorescent pigment, or anycombination thereof) having a melt-emulsified morphology.

Clause 2. The composition of Clause 1, wherein the melt-emulsifiedmorphology comprises the pigment having a coating comprising thethermoplastic polymer and the coated pigment is adhered to an outersurface of a thermoplastic polymer particle.

Clause 3. The composition of Clause 2, wherein the coating has anemulsion stabilizer coating.

Clause 4. The composition of Clause 1, wherein the melt-emulsifiedmorphology comprises the pigment being embedded in an outer surface of athermoplastic polymer particle.

Clause 5. The composition of Clause 1, wherein the melt-emulsifiedmorphology comprises the pigment being encapsulated by a thermoplasticpolymer particle.

Clause 6. The composition of Clause 1 further comprising the pigmenthaving a coating and not being adhered to, embedded in, or encapsulatedby with a thermoplastic polymer particle.

Clause 7. The composition of Clause 6, wherein the coating of thepigment has an emulsion stabilizer coating.

Clause 8. The composition of Clause 1, wherein the pigmented polymerparticles have a circularity of about 0.90 to about 1.0.

Clause 9. The composition of Clause 1, wherein the pigmented polymerparticles have an emulsion stabilizer coating at least a portion of anouter surface of the pigmented polymer particles.

Clause 10. The composition of Clause 9, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles, and wherein at least someof the emulsion stabilizer is embedded in the outer surface of thepigmented polymer particles.

Clause 11. The composition of Clause 9, wherein at least some of thepigmented polymer particles have a void comprising the emulsionstabilizer at a void/polymer interface.

Clause 12. The composition of Clause 11, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles are embedded in thevoid/polymer interface.

Clause 13. The composition of Clause 11, wherein the void contains thecarrier fluid.

Clause 14. A method comprising: depositing, upon a surface, thepigmented polymer particles of Clause 1 optionally in combination withother thermoplastic polymer particles; and once deposited, heating atleast a portion of the particles to promote consolidation thereof andform a consolidated body.

Clause 15. A composition comprising: pigmented polymer particlescomprising a thermoplastic polymer and a pigment (e.g., colored pigment,metallic pigment, pearlescent pigment, phosphorescent pigment, or anycombination thereof), wherein at least some of the pigmented polymerparticles have a morphology according to (a), (b), (c), or anycombination thereof: (a) the pigment having a coating comprising thethermoplastic polymer and the coated pigment adhered to a thermoplasticpolymer particle, (b) the pigment being embedded in an outer surface ofthe thermoplastic polymer particle, and (c) the pigment beingencapsulated by the thermoplastic polymer particle.

Clause 16. The composition of Clause 15, wherein (a) morphology ispresent and the coating of the pigment has an emulsion stabilizercoating.

Clause 17. The composition of Clause 15 further comprising the pigmenthaving a coating and not being adhered to, embedded in, or encapsulatedby with a thermoplastic polymer particle.

Clause 18. The composition of Clause 17, wherein the coating of thepigment has an emulsion stabilizer coating.

Clause 19. The composition of Clause 15, wherein the pigmented polymerparticles have a circularity of about 0.90 to about 1.0.

Clause 20. The composition of Clause 15, wherein the pigmented polymerparticles have an emulsion stabilizer coating at least a portion of anouter surface of the pigmented polymer particles.

Clause 21. The composition of Clause 20, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles, and wherein at least someof the emulsion stabilizer is embedded in the outer surface of thepigmented polymer particles.

Clause 22. The composition of Clause 20, wherein at least some of thepigmented polymer particles have a void comprising the emulsionstabilizer at a void/polymer interface.

Clause 23. The composition of Clause 22, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles are embedded in thevoid/polymer interface.

Clause 24. The composition of Clause 22, wherein the void contains thecarrier fluid.

Clause 25. A method comprising: depositing, upon a surface, thepigmented polymer particles of Clause 1 optionally in combination withother thermoplastic polymer particles; and once deposited, heating atleast a portion of the particles to promote consolidation thereof andform a consolidated body.

Clause 26. A method comprising: mixing a mixture comprising athermoplastic polymer, a carrier fluid that is immiscible with thethermoplastic polymer, a pigment (e.g., colored pigment, metallicpigment, pearlescent pigment, phosphorescent pigment, or any combinationthereof), and optionally an emulsion stabilizer at a temperature greaterthan a melting point or softening temperature of the thermoplasticpolymer and at a shear rate sufficiently high to disperse thethermoplastic polymer in the carrier fluid; cooling the mixture to belowthe melting point or softening temperature of the thermoplastic polymerto form pigmented polymer particles comprising a thermoplastic polymerand a pigment having a melt-emulsified morphology; and separating thepigmented polymer particles from the carrier fluid.

Clause 27. A method comprising: mixing a mixture comprising athermoplastic polymer, a carrier fluid that is immiscible with thethermoplastic polymer, a pigment (e.g., colored pigment, metallicpigment, pearlescent pigment, phosphorescent pigment, or any combinationthereof), and optionally an emulsion stabilizer at a temperature greaterthan a melting point or softening temperature of the thermoplasticpolymer and at a shear rate sufficiently high to disperse thethermoplastic polymer in the carrier fluid; cooling the mixture to belowthe melting point or softening temperature of the thermoplastic polymerto form pigmented polymer particles comprising a thermoplastic polymerand a pigment, wherein at least some of the pigmented polymer particleshave a morphology according to (a), (b), (c), or any combinationthereof: (a) the pigment having a coating comprising the thermoplasticpolymer and the coated pigment adhered to a thermoplastic polymerparticle, (b) the pigment being embedded in an outer surface of thethermoplastic polymer particle, and (c) the pigment being encapsulatedby the thermoplastic polymer particle; and separating the pigmentedpolymer particles from the carrier fluid.

Clause 28. The method of Clause 26 or 27, wherein the pigment is a firstpigment, and wherein the mixture further comprises a second pigmentdifferent than the first pigment.

Clause 29. The method of Clause 26 or 27, wherein the pigmented polymerparticles comprise 0.01 wt % to 30 wt % of the pigment based on theweight of the thermoplastic polymer in the pigmented polymer particles.

Clause 30. The method of Clause 26 or 27, wherein the emulsionstabilizer is included in the mixture, and wherein the emulsionstabilizer coating at least a portion of an outer surface of thepigmented polymer particles.

Clause 31. The method of Clause 30, wherein the emulsion stabilizer isembedded in the outer surface.

Clause 32. The method of Clause 26 or 27, wherein the pigmented polymerparticles have a D10 of about 0.1 μm to about 125 μm, a D50 of about 0.5μm to about 200 μm, and a D90 of about 3 μm to about 300 μm, whereinD10<D50<D90.

Clause 33. The method of Clause 26 or 27, wherein the pigmented polymerparticles have a diameter span of about 0.2 to about 10.

Clause 34. The method of Clause 26 or 27, wherein the pigmented polymerparticles have a circularity of about 0.90 to about 1.0.

Clause 35. The method of Clause 26 or 27, wherein the pigmented polymerparticles have a Hausner ratio of about 1.0 to about 1.5.

Clause 36. The method of Clause 26 or 27, wherein the melt-emulsifiedmorphology comprises the pigment having a coating comprising thethermoplastic polymer and the coated pigment is adhered to an outersurface of a thermoplastic polymer particle.

Clause 37. The method of Clause 26 or 27, wherein the melt-emulsifiedmorphology comprises the pigment being embedded in an outer surface of athermoplastic polymer particle.

Clause 38. The method of Clause 26 or 27, wherein the melt-emulsifiedmorphology comprises the pigment being encapsulated by a thermoplasticpolymer particle.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, process conditions,and so forth used in the present specification and associated claims areto be understood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained by the embodiments of the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claim, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

One or more illustrative embodiments incorporating the inventionembodiments disclosed herein are presented herein. Not all features of aphysical implementation are described or shown in this application forthe sake of clarity. It is understood that in the development of aphysical embodiment incorporating the embodiments of the presentinvention, numerous implementation-specific decisions must be made toachieve the developer's goals, such as compliance with system-related,business-related, government-related and other constraints, which varyby implementation and from time to time. While a developer's effortsmight be time-consuming, such efforts would be, nevertheless, a routineundertaking for those of ordinary skill in the art and having benefit ofthis disclosure.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsand steps.

To facilitate a better understanding of the embodiments of the presentinvention, the following examples of preferred or representativeembodiments are given. In no way should the following examples be readto limit, or to define, the scope of the invention.

EXAMPLES

Control Sample 1-1. To a 500 mL glass reactor 117 g of PDMS (PSF™ 30,000cSt available from Clearco) was added. Using approximately 20 g of themeasured PDMS, a slurry was made by mixing the PDMS with 0.75 g AEROSIL®RX50 fumed silica. This slurry was added to the glass reactor followedby 50 g of polypropylene homopolymer resin (ULTRA HOPP™ 20 fromResMart). The reactor was set to 150 revolutions per minute (rpm) withone P4 shaft and heated to 250° C. Once the temperature was reached, therpm was increased to 500. After 30 min, the melt was discharged into ametal container containing dry ice. Once the dry ice sublimated, themelt was then washed thrice with heptane and isolated by vacuumfiltration. The particles were dried overnight in a vacuum oven at roomtemperature and then sieved through a 250 μm screen.

Control Sample 1-2. The procedure for Control Sample 1-1 was repeated.The resulting particles were dry blended with 15 wt % pigment powderusing a high intensity powder mixer operating at about 13,500 rpm forabout 30 seconds. The pigment was GloTech International GT8400 Naturalpigment, which has a D50 less than 25 μm.

Sample 1-1. The procedure for Control Sample 1-1 was repeated with theexception that 5 wt % pigment was added after the addition of the RX50fumed silica and mixed until the reactor reached temperature.

Sample 1-2. The procedure for Sample 1-1 was repeated with the exceptionthat 10 wt % pigment was added.

Sample 1-3. The procedure for Sample 1-1 was repeated with the exceptionthat 15 wt % pigment was added.

Table 1 provides the properties of the produced samples.

TABLE 1 Control Control Sample Sample Sample Property Sample 1-1 Sample1-2 1-1 1-2 1-3 Pigment 0 15 5 10 15 Loading (dry blend) (wt %) D50,54.4 52.5 54.2 64.7 66.2 unsieved (μm) Span, 2.0 1.3 1.1 1.0 1.0unsieved D50, sieved 52.3 48.8 53.4 64.3 65.8 (μm) Span, sieved 1.0 1.20.9 0.9 0.9 Angle of 30.4 36.6 37.5 40.2 40.4 Repose (°)

FIGS. 2 and 3 are scanning electron micrographs of Samples 1-2 and 1-3,respectively, illustrating polymer coated pigment being adhered to asurface of the polymer particle. FIGS. 4 and 5 are cross-sectionalscanning electron micrographs (samples fixed in epoxy resin andcryo-microtomed before imaging) of Sample 1-2 illustrating (a) pigmentnot adhered to, embedded in, or encapsulated by a polymer particle and(b) pigment embedded in a surface of a polymer particle.

The samples were 3D printed on a SNOWWHITE SLS printer (available fromSharebot). A 30 mm×30 mm×0.1 mm square was printed as a preliminaryscreening object. Briefly, the sieved particles were applied onto analuminum plate using a bar coater (40 mil gap/approximately 1 mm thicklayer of powder). The sample was placed in the SNOWWHITE chamber. Themotors were disabled since a multilayer object was not printed. Thechamber temperature was set to 115° C. Laser rate and laser power werevaried to determine optimal print conditions. The chamber and powder bedwere cooled to room temperature before the part was removed. Table 2provides the printing parameters and properties of the resultant printedsquares.

TABLE 2 Control Control Sample Sample Sample Sample Sample 1-1 1-2 1-11-2 1-3 Laser 40,000 40,000 40,000 40,000 40,000 Rate Laser 60%-80%35%-70% 50%-80% 60%-80% 60%-80% Power Range Percent 0.1%-0.9%   0%-0.2%0.5%-3.4% 0.8%-1.9% 0.8%-1.4% Void Range Edge 0.6 1.3 0.8 0.4 0.4 Curl

Control Sample 2-1. To a 500 mL glass reactor 117 g of PDMS (PSF™ 30,000cSt available from Clearco) was added. Using approximately 20 g of themeasured PDMS, a slurry was made by mixing the PDMS with 0.75 g AEROSIL®RX50 fumed silica. This slurry was added to the glass reactor followedby 50 g of polypropylene homopolymer resin (ULTRA HOPP™ 20 fromResMart). The reactor was set to 150 revolutions per minute (rpm) withone P4 shaft and heated to 250° C. Once the temperature was reached, therpm was increased to 500. After 30 min, the melt was discharged into ametal container containing dry ice. Once the dry ice sublimated, themelt was then washed thrice with heptane and isolated by vacuumfiltration. The particles were dried overnight in a vacuum oven at roomtemperature and then sieved through a 250 μm screen.

The resulting particles were dry blended with 15 wt % pigment powderusing a high intensity powder mixer operating at about 13,500 rpm forabout 30 seconds. The pigment was ULTRAGLOW™ pigment (europium-basedphosphorescent powder, available from Aqua Glow), which has a D50 ofabout 28 μm.

Sample 2-1. The procedure for Control Sample 2-1 was repeated with theexception that 15 wt % pigment was added after the addition of the RX50fumed silica and mixed until the reactor reached temperature.

Table 3 provides the properties of the produced samples.

TABLE 3 Property Control Sample 2-1 Sample 2-1 Pigment Loading (wt %) 15(dry blend) 15 D50, unsieved (μm) couldn't measure 91.8 Span, unsievedcouldn't measure 1.4 D50, sieved (μm) couldn't measure 92.4 Span, sievedcouldn't measure 1.0 Angle of Repose (°) didn't measure 41.0

A 30 mm×30 mm×0.1 mm square was printed as described above for Sample2-1 with a SNOWWHITE SLS printer. There was not enough of Control Sample2-1 for printing. Table 4 provides the properties of the resultantprinted squares.

TABLE 4 Sample 2-1 Laser Rate 40,000 Laser Power Range 80%-85% PercentVoid Range 2.8%-6.3% Edge Curl 0.4

Sample 3-1. To a 500 mL glass reactor 117 g of PDMS (PSF™ 10,000 cStavailable from Clearco) was added. Using approximately 20 g of themeasured PDMS, a slurry was made by mixing the PDMS with 0.5 g AEROSIL®RX50 fumed silica. This slurry was added to the glass reactor followedby 15 wt % pigment (GT8400 Natural pigment, available from GloTechInternational) and 50 g of polyamide-12 homopolymer resin (RTP 200 F,available from RTP). The reactor was set to 250 revolutions per minute(rpm) and heated to 220° C. Once the temperature was reached, the rpmwas increased to 1000. After 30 min, the melt was allowed to cool on thebench. Once cooled, the melt was then washed thrice with heptane andisolated by vacuum filtration. The particles were dried overnight in avacuum oven at room temperature and then sieved through a 250 μm screen.

Table 5 provides the properties of the produced samples.

TABLE 5 Property Sample 3-1 Pigment Loading (wt %) 15 D50, unsieved (μm)162.0 Span, unsieved 2.7 D50, sieved (μm) 130.0 Span, sieved 1.3 Angleof Repose (°) 30.1

FIGS. 6 and 7 are scanning electron micrographs of Sample 3-1illustrating what is likely polymer coated pigment being adhered to asurface of the polymer particle. FIGS. 8 and 9 are cross-sectionalscanning electron micrographs (samples fixed in epoxy resin andcryo-microtomed before imaging) illustrating (a) pigment embedded in asurface of the polymer particle and (b) pigment encapsulated in thepolymer particle. Energy dispersive x-ray spectroscopy of FIG. 9 theencapsulated particles comprise strontium and are, therefore, thepigment.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein. Theparticular embodiments disclosed above are illustrative only, as thepresent invention may be modified and practiced in different butequivalent manners apparent to those skilled in the art having thebenefit of the teachings herein. Furthermore, no limitations areintended to the details of construction or design herein shown, otherthan as described in the claims below. It is therefore evident that theparticular illustrative embodiments disclosed above may be altered,combined, or modified and all such variations are considered within thescope and spirit of the present invention. The invention illustrativelydisclosed herein suitably may be practiced in the absence of any elementthat is not specifically disclosed herein and/or any optional elementdisclosed herein. While compositions and methods are described in termsof “comprising,” “containing,” or “including” various components orsteps, the compositions and methods can also “consist essentially of” or“consist of” the various components and steps. All numbers and rangesdisclosed above may vary by some amount. Whenever a numerical range witha lower limit and an upper limit is disclosed, any number and anyincluded range falling within the range is specifically disclosed. Inparticular, every range of values (of the form, “from about a to aboutb,” or, equivalently, “from approximately a to b,” or, equivalently,“from approximately a-b”) disclosed herein is to be understood to setforth every number and range encompassed within the broader range ofvalues. Also, the terms in the claims have their plain, ordinary meaningunless otherwise explicitly and clearly defined by the patentee.Moreover, the indefinite articles “a” or “an,” as used in the claims,are defined herein to mean one or more than one of the element that itintroduces.

What is claimed:
 1. A method comprising: providing a mixture comprisinga thermoplastic polymer, a carrier fluid that is immiscible with thethermoplastic polymer, a pigment, and an emulsion stabilizer; whereinthe emulsion stabilizer comprises nanoparticles selected from the groupconsisting of oxide nanoparticles, polymer nanoparticles, and anycombination thereof; applying shear to the mixture at a temperaturegreater than a melting point or softening temperature of thethermoplastic polymer and at a shear rate sufficiently high to dispersethe thermoplastic polymer in the carrier fluid as droplets; cooling themixture to below the melting point or softening temperature of thethermoplastic polymer to form pigmented polymer particles comprising thethermoplastic polymer, the pigment, and the nanoparticles, wherein thenanoparticles are coated upon an outer surface of the pigmented polymerparticles, and wherein at least some of the pigmented polymer particleshave a morphology according to (a), (b), (c), or any combinationthereof: (a) the pigment being coated by the thermoplastic polymer todefine a coated pigment, and the coated pigment being adhered to theouter surface, (b) the pigment being embedded in the outer surface, and(c) the pigment being encapsulated by the thermoplastic polymer belowthe outer surface; and separating the pigmented polymer particles fromthe carrier fluid; wherein the pigmented polymer particles have a D10 ofabout 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200 μm, anda D90 of about 3 μm to about 300 μm, wherein D10<D50<D90.
 2. The methodof claim 1, wherein the pigment comprises a first pigment and a secondpigment that are different from one another.
 3. The method of claim 1,wherein the pigmented polymer particles comprise 0.01 wt % to 30 wt % ofthe pigment based on a weight of the thermoplastic polymer in thepigmented polymer particles.
 4. The method of claim 1, wherein thenanoparticles are embedded in the outer surface.
 5. The method of claim1, wherein the pigmented polymer particles have a diameter span of about0.2 to about
 10. 6. The method of claim 1, wherein the pigmented polymerparticles have a circularity of about 0.90 to about 1.0.
 7. The methodof claim 1, wherein the pigmented polymer particles have a Hausner ratioof about 1.0 to about 1.5.
 8. The method of claim 1, wherein thenanoparticles comprise silica nanoparticles.
 9. A method comprising:providing a mixture comprising a thermoplastic polymer, a carrier fluidthat is immiscible with the thermoplastic polymer, a pigment, and anemulsion stabilizer; wherein the emulsion stabilizer comprisesnanoparticles selected from the group consisting of oxide nanoparticles,polymer nanoparticles, and any combination thereof; and wherein thecarrier fluid is selected from the group consisting of a silicone oil, afluorinated silicone oil, a perfluorinated silicone oil, a polyethyleneglycol, an alkyl-terminal polyethylene glycol, tetraethylene glycoldimethyl ether, a paraffin, a liquid petroleum jelly, a vison oil, aturtle oil, a soya bean oil, perhydrosqualene, a sweet almond oil, acalophyllum oil, a palm oil, a parleam oil, a grapeseed oil, a sesameoil, a maize oil, a rapeseed oil, a sunflower oil, a cottonseed oil, anapricot oil, a castor oil, an avocado oil, a jojoba oil, an olive oil, acereal germ oil, an ester of lanolic acid, an ester of oleic acid, anester of lauric acid, an ester of stearic acid, a fatty ester, a fattyacid, a fatty alcohol, a polysiloxane modified with fatty acids, apolysiloxane modified with fatty alcohols, a polysiloxane modified withpolyoxyalkylenes, and any combination thereof; applying shear to themixture at a temperature greater than a melting point or softeningtemperature of the thermoplastic polymer and at a shear ratesufficiently high to disperse the thermoplastic polymer in the carrierfluid as droplets; cooling the mixture to below the melting point orsoftening temperature of the thermoplastic polymer to form pigmentedpolymer particles comprising the thermoplastic polymer, the pigment, andthe nanoparticles, wherein the nanoparticles are coated upon an outersurface of the pigmented polymer particles, and wherein at least some ofthe pigmented polymer particles have a morphology according to (a), (b),(c), or any combination thereof: (a) the pigment being coated by thethermoplastic polymer to define a coated pigment, and the coated pigmentbeing adhered to the outer surface, (b) the pigment being embedded inthe outer surface, and (c) the pigment being encapsulated by thethermoplastic polymer below the outer surface; and separating thepigmented polymer particles from the carrier fluid.
 10. The method ofclaim 1, wherein the pigmented polymer particles have a diameter span ofabout 0.2 to about 1.2.